Electrodeposition of nickel



l at e'n teci July 7,

, UNITE PATENT OFFICE f f amass ELEo'monE'nosrrIoN F NICKEL WiiburfJ sh eaiejxigzyshaker Heights, drift; is

signer toTh'ef Harshaw Chemical Company, lleveland Ohio}; corporation of Ohio I No ama Application March 31, 1951,

Serial-No. 218,693

6 Claims. (01. acme This inventionrelates to electrodepositionof metals, and more specifically to a process of, and solutions for, use in a process of electrodeposit ing nickel, characterized in that the resultingt' nickel electrodeposit. is bright as it comes from the plating solution, is veryductile and very smooth. More particularly,,thepresent invention has to do with the discovery of cooperating addition agents suitable for use in an aqueous,

acid. nickel plating; solution; and having the capability of producing. electrodepo'sit's; of unusual brilliance on comparatively rough surfaces accompanied by extreme ductility andincrease in smoothnessover the: base. metal. i

Many-ofathe so-called bright plating solutions are capable of producing deposits of extreme brilliance when the deposit is made on-very 'high'--- 1y polished base. metal, such as polished brass, but produce less impressive deposits'on rougher surfaces, suchascsteel or: brass, which has been bufied with abrasive leavingasurf,ace-which has,

some sheen but is not highly polished'. an object ofthe present invention to provide a solu tion capableof producingsdeposits of full brightness on surfaces which are.less than fully polished as. will beiindicated on a' quantitativeba-sis hereinafterfi iIt isa furtherflobjecttov produce depos, itswhich'fare extremely ductile and which on" base. surfaces of some; degree? of. roughness; are smoother than the baselmetal" itself ';.'that is,* the deposit builds smoothness ratherthan becoming lesssmooth with increasing thickness flas"is'"the case with somebright deposits.

I have now diseciveredthatthe foregoirigblf jects can be attained in surprising degreeby the use in an aqueous; acid; nickel'platlng solution made'up essentially of a nickel electrolyte oi the class consisting of nickel sulfate, nickel chloride, and mixtures of nickel sulfate with nickel chloride, and an efiectiveeamount ofleach of two cooperating additionagents; oneof such addition'agents being selected from the class consisting of compounds represented by the -for i H 2 ,1? ewes tacos:

and salts and hydrates thereof, a being an integer from 1 to 3, where R representsa radicalselected' from the class consisting ofhydrogemchlorine, bromine, methyl, ethyl, propyl, butyl, cyclohexyl, isopropyl, and phenyl, and R represents a" radical'selected from the class consistingofhyand R7; taken tdgetheri represent a bi- Valenti radical} select Efrem the class consisting of me'i'hylidehe} ethy i dene;- propylidene', f isopropyliden'ei-and butylidene; for'example' a -rb -t xym ir y e m these .7 I

a (2)} 1-(l."-carboxyl-Pphenylmetliyl) pyridinium,

m n. merge,

(i) '1 -(1-earb oxyisobutyl)g py'ridinium broifiideg I (k) l l '-carboxybutyl); pyridinium bromide},

of msre mum where is selected from the classrconsistingiof OH, NHa, NHSOzPh, NHSO: alkyl (1 to 12 carbon atoms), chloro and bromo substitution products,

andfnickel', iron, 'cobalt, sodium, and potassium salts of the foregoing as 'well as saccharine and 7 its correspondingssaltsi.

Examples of' the'se addition agents are as follows: g e

1}; Diben'zene'sulfonamide 3. saccharine 4 The constituents of the bath according to the preferred practice of invention are: (1) water, (2) nickel sulfate, nickel chloride, or nickel sulfate with nickel chloride, (3) an aromatic sulfur NH 5 compound of the class defined such as benzene sulfonate, soluble saccharine, dibenzene sulfonamide, or the like, and a pyridinium carboxylate Benzene summit, acid compound of the class defined. An additional ingredient of the solution which is desirable is 10 abuifering agent such as boric acid, formic acid, @5038 or the like. It will be noted that in respect to major constituents, the solutions are similar to 5. Benzene sulfonamide the well-known all-sulfate, all-chloride, and "sulfate-chloride," or Watts type nickel plating solutions. fsomm The preferred basic solutions in connection with which the invention is realized are as 101- The nickel, iron, cobalt, sodium, and potassium lows! salts of the foregoing are substantially equivalent no l Sulfate and can be used with q y good results- 4 NiS0 7H O 100 t 400 gms preferably It will be seen that the addition agents of the 200 to 300 i'ns. first-mentioned type are pyridinium carboxylate Bone 0 {8 6 3 Preferably compounds having one or more carbon atoms in- Wetting agent (e. g. sodium 0 to 5 gms, preferably 0.5 terposed between the nitrogen atom of the pyg g g eggg k 3% 1. ridinium radical and the carboxy group. Substiu tution in the side chain can be made freely as All chllmde indicated, whereas substitution on the pyridinium MCIWGHHO to 250 gm preferably ring appears to impair the usefulness of the 100 to 200 iiis. compound. The quaternary nitrogen atom is the 0 5% g? 5 essential point of attachment of the side chain. Wetting agent (e. g. sodium 0 to 5 gma, preferably 0.5

As will be seen, the addition agents of the secf f 5% ond-mentioned class'are sulfonates, sulfonam- 5 ides, sulfonimides, and sulfonic acids having one sulfate-c ide ai s ype) r m re ar matic r n s of th b n ne typ hat Nisoflmo to 400 preferably is, having a single-ring or benzene nucleus. Sub- 5 200 to 350 gins. stitutions may be made on the ring of various N1C12'6H20 g gf g f Preferably groups such as alkyl (1 to 12 carbon atoms), Boric acid o {g eo mel' refemm halogen (chlorine, bromine),-and the like. e 4 Addition agents of the pyridinium carboxylate 133 3 1 f e Sodlum oi m i gi iff' prefemm 3 3??? ll3$tii$filftifelfitiififi eeee ef e feeeeelee eeee eeleeeee I eee agents of the second class are employed in cong r gig i g g g z gggg g o w co p 1 a 1 n fiirgltrations of the order of .5 to 2.5 grams per agents f 31 of saiiladtfiontagents ggl gfi It is to be understood that all statements made i5 i one o 8 .Pi 5 an e 0 er herein concerning the capabilities of the addition 15 9 the pyndmmm carbylate type both agents presuppose the use of one or a mixture scribed above. The solution may contain an of two or more from each class; that is one or anti-pit agent although the deposits usually will more of the pyridinium carboxylate compounds be sulta'ble for many purposes f other. together with one or more of the aromatic sulfur so afidmon agent for eliminating the p1tt1ng- Q compounds. For convenience the pyridinium dlum lauryl sulfate may be used as an anm'plt carboxylate compounds are considered to be agent although as stated use 15 not ordibrighteners, and the aromatic sulfur compounds nalny essential, and other Wettmg agents are considered to be carriers or auxiliary brightu s of Wett ng agents may be used for control eners, although actually they are cooperating of pitting. brighteners and either may be regarded as aux- The following specific examples will serve t iliary to the other. illustrate the invention:

Solution No 1 g 3 4 l 6 7 i 8 9 Nickel suime-esio g./l..

Nickel Chloride-H1 0 Sodium Lauryl tc Ethanesulfonyl Benzene Suli'onamide Carboxymethyl Benzene Sulfonamide- Dibenzenc Sulionamide N-(l-Carboxy-n-amyl) Pyridinium Bro .g./l N-(3Carboxy Propyl) Pyridlnium Bromidc.g./l N-(ZCarboxy Propyl) Pyridinium Bromide g./l. Saccharine (Sodium Salt) g./l..

pH Temperature (Degrees Fahrenheit).

o. 1)., AmpsJSq. Ft .-I

of the irregularities in the surface thereof'from the average surface plane is about to microinches, and the thickness of the deposit is about 0.001, which method comprises electrolyzing an aqueous, acid solution of a nickel electrolyte of the class consisting of nickel sulfate, nickel chloride, and mixtures of nickel sulfate with nickel chloride, said solution also containing cooperating addition agents capable of imparting brightness and smoothing power as aforesaid, one of said addition agents being a pyridinium carboxylate compound selected from the class consisting of l-(carboxymethyl) pyridinium chloride, 1 (carboxymethyl) pyridinium bromide, 1(1carboxyamyl) pyridinium bromide, 1-(1'- carboxypropyl) pyridinium bromide, 1-(1-carboxy 1' phenylmethyl) pyridinium bromide, 1-(1'-carboxyethyl) pyridinium chloride, l-(l carboxyvinyl) pyridinium bromide, l-(2'-carboxyethyl) pyridinium chloride, l-(2'-carboxypropyl) pyridinium chloride, l-(l-carboxyisobutyl) pyridinium bromide, l-(1'-carboxybutyl) pyridinium bromide, and 1-(3'-carboxypropyl) pyridinium bromide, and the second of said addi-- tion agents being an aromatic sulfur compound selected from the group consisting of compounds of the formula ArSOzR, where Ar is selected from the class consisting of benzene and naphthalene radicals and R is selected from the class consisting of OH, NHz, NHSOzPh, NHSO: alkyl wherein the alkyl group contains from 1 to 12 carbon atoms, and chloro and bromo substitution products of said compounds and the nickel, iron, cobalt, sodium and potassium salts of the foregoing.

2. A method of eleotrodepositing nickel on a metallic surface in the form of a deposit which is bright as taken from the plating, solution without further treatment, and which is ductile and smoother than said metallic surface when the root mean square average deviation of the irregularities in the surface thereof from the averagesurface plane is about 10 to 15 microinches, and the thickness of the deposit is about 0.0015, which method comprises electrolyzing an aqueous, acid solution of a nickel electrolyte of the class consisting of nickel sulfate, nickel-chloride, and mixtures of nickel sulfate with nickel chloride, said solution also containing cooperating addition agents capable of imparting brightness and smoothing power as aforesaid, one of said addition agents being l-(carboxymethyD pyridinium chloride and being present in concentration from 0.1 to 1.0 gram per liter, and the other of said addition agents being dibenzene sulfonamide and being present in concentration from 0.5 to 2.5 grams per liter.

3. A method of electrodepositi'ng nickel on a.

metallic surface in the form of a deposit which is bright as taken from the plating solution without further treatment and which is ductile and smoother than said metallic surface when the root mean square average deviation of the irregularities in the surface thereof from the average surface plane is about 10 to 15 microinches, and the thickness of the deposit is about 0.001, which method comprises electrolyzing' an: aqueous, acid solutiozrof a nickel electrolyteof the class con sisting of nickel sulfate, nickel'chloride, and mix-- tures of nickel sulfate with nickel chloride, said solution also containing cooperating, addition agents capable of imparting brightness and smoothing power asafQr'esaid; one of said addition agents being l-,(1'-ca,rboxyvinyl) pyridinium chloride and being present inconcentration from- 0.1 to ILUgram per liter, 'an'dthe other offsaid addition agents being dibenzene sulfonamide and being present in concentration from 0.5 to 2.5 grams per liter.

4. A method of electrodepositing nickel on a metallic surface in the form of a deposit which is bright astaken from the plating solution without further treatment, and which'is ductile and smoother than said metallic surface when the root mean square average deviation of the irregularities in the surface thereof from the average surface plane is about 10 to 15 microinches, and the thickness of the deposit is about 0.001, which method comprises electrolyzing an aqueous, acid solution-of a nickel electrolyte of the class consisting of nickel sulfate, nickel chloride, and mix-..

tures of nickel sulfate with nickelchloride, said solution also containing cooperating addition agents capable of imparting brightness and smoothing-power as aforesaid, one of said addition agents being 1-(2'-carboxyethyl) pyridinium chloride and being present in concentration from 0.1 to 1,0 gram per liter, and the other of said addition agents being dibenzene sulfonamide and being present in concentration from 0.5 to 2.5

grams per liter.

5. A -method of electrodepositing nickel on a metallic surface in the form of a deposit which is bright as taken from the plating solution without further treatment, and which is ductile and smoother than said metallic surface when the root mean square average deviation of the irregularities in the surface thereof from theaverage surface plane is about 10 to 15 microinches, and the thickness of the deposit is about 0.001", which method comprises electrolyzing anaqueous, acid solution of a nickel electrolyte of the class consisting of nickel sulfate, nickel chloride, and mix- I tures of nickel sulfate with nickel chloride, said solution also containing cooperating addition agents capable of imparting brightness and smoothing power as aforesaid, one of said addi-' tion agents being l-(carboxymethyl) pyridinium chloride and being present in concentration from 0.1 to 1.0 gram per liter, and the other of said addition agents being ethane sulfonyl benzene sulfonamidev and beingpresent in concentration from 0.5 to 2.5 grams per liter.

6. A method of electrodepositing nickelon a metallic surface in the form of a deposit which is bright as takenfrom the. plating solution without further treatment, and which is ductile and smoother than said metallic surface when the root mean square average deviation of the irregularities in the surface thereof from the average surface plane is about 10 to 15 microinches, and the thickness of the deposit is about 0.001", which method comprises electrolyzing an aqueous, acid solution of a nickel electrolyte of the class consisting of nickel sulfate, nickel chloride, and mixtures of nickel sulfate with nickel chloride, said solution also containing cooperating addition agents capable of imparting brightness and smoothing power as aforesaid, one of said addition agents being l-(carboxymethyl) pyridinium chloride and being present in concentration from I 8 0.1 to 10 gram per liter, and the other '0! said Number Name Date addition agents being saccharine and being pres- 2,513,280 Brown July 4, 1950 ent in concentration from 0.5 to 2.5 grams per 2,550,449 Brown Apr. 24, 1951 OTHER REFERENCES WILBUR J. SHENK, JR. 5

Raub et a1., Metal Fmishing, August 1940, pp.

References Cited in the file of this patent 429-432.

UNITED STATES PATENTS Silman, Metal Industry, November 24, 1944, pp.

330-332. Number Name Date 10 2,315,802 Lind et a1 Apr. 6, 1943 

1. A METHOD OF ELECTRODEPOSITING NICKEL ON A METALLIC SURFACE IN THE FORM OF A DEPOSIT WHICH IS BRIGHT AS TAKEN FROM THE PLATING SOLUTION WITHOUT FUTHER TREATMENT, AND WHICH DEPOSIT IS DUCTILE AND SMOOTHER THAN SAID METALLIC SURFACE WHEN TH ROOT MEAN SQUARE AVERAGE DEVIATION OF THE IRREGULARITIES IN THE SURFACE THEREOF FROM THE AVERAGE SURFACE PLANE IS ABOUT 10 TO 15 MICROINCHES, AND THE THICKNESS OF THE DEPOSIT IS ABOUT 0.001" WHICH METHOD COMPRISES ELECTROYLYZING AN AQUEOUS, ACID SOLUTION OF A NICKEL ELECTROLYTE OF THE CLASS CONSISTING OF NICKEL SULFATE, NICKEL CHOL RIDE, AND MIXTURES OF NICKEL SULFATE WITH NICKEL CHLORIDE, SAID SOLUTION ALSO CONTAINING COOPERATING ADDITION AGENTS CAPABLE OF IMPARTING BRIGHTNESS AND SMOOTHING POWER AS AFORESAID, ONE OF SAID ADDITION AGENT BEING A PYRIDINIUM CARBOXYLATE COMPOUND SELECTED FROM THE CLASS CONSISTING OF 1-(CARBOXYMETHYL) PYRIDINIUM CHLORIDE, 1-(CARBOXYMETHYL) PYRIDINIUM BROMIDE, 1-(1''-CARBOXYAMYL) PYRIDINIUM, 1-(1''CARBOXYPROPYL) PYRIDINIMUM BROMIDE, 1-(1''-CARBOXY - 1'' - PHENYIMETHYL) PYRIDINIUM BROMIDE, 1-(1''-CARBOXYETHYL) PRYIDINIUM CHLORIDE, 1-(1''CARBOXYVINYL) PYRIDINIUM BROMIDE, 1-(2''-CARBOXYETHYL PYRIDINIUM CHLORIDE, 1-(2''-CARBOXYPROPYL) PYRIDINIUM CHLORIDE, 1-(1''-CARBOXYISOBUTYL) PYRIDINIUM BROMIDE, 1-(1''-CARBOXYBUTYL) PYRIDINIUM BROMIDE, AND 1-3''-CARBOXYPROPYL) PYRIDINIUM BROMIDE, AND THE SECOND OF SAID ADDITION AGENTS BEING AN AROMATIC SULFUR COMPOUND SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS OF THE FORMULA ARSOR2R, WHERE AR IS SELECTED FROM THE CLASS CONSISTING OF BENZENE AND NAPHTHALENE RADICALS AND R IS SELECTED FROM THE CLASS CONSISTING OF OH, NH2, NHSO2PH, NHSO2 ALKYL WHEREIN THE ALKYL GROUP CONTAINS FROM 1 TO 12 CARBON ATOMS, AND CHLORO AND BROMO SUBSTITUTION PRODUCTS OF SAID COMPOUNDS AND THE NICKEL, IRON, COBALT, SODIUM AND POTASSIUM SALTS OF THE FOREGOING. 